The invention relates to a process for the preparation of a hydrocarbon mixture having a Ramsbottom Carbon Test value (RCT) of (a) %w and an initial boiling point of T.sub.1 .degree.C.
The RCT is an important parameter in the assessment of the suitability of heavy hydrocarbon mixtures as feedstocks for catalytic conversion processes, such as catalytic cracking, carried out in the presence or absence of hydrogen, for the preparation of light hydrocarbon distillates, such as gasoline and kerosine. According as the feed has a higher RCT, the catalyst will be deactivated more rapidly in these processes.
Residual hydrocarbon mixtures, such as residues obtained in the distillation of a crude mineral oil and asphaltic bitumen separated in the solvent deasphalting of the said distillation residues or of residues obtained in the distillation of a hydrotreated residual fraction of a crude mineral oil generally have too high an RCT to be suitable without previous treatment for use as feeds for the above-mentioned catalytic conversion processes. Since the RCT of residual hydrocarbon mixtures is mainly determined by the percentage of asphaltenes present in the mixtures, a reduction of the RCT of these mixtures can be obtained by reducing the asphaltenes content. Basically, this may be achieved in two ways. Part of the asphaltenes may be separated from the mixture by solvent deasphalting, or part of the asphaltenes may be converted by subjecting the mixture to a catalytic hydrotreatment. For the reduction of the RCT of distillation residues the latter method is preferred, in the first place, because its yield of heavy product with a low RCT is higher and further because, in contrast to the former method, where asphaltic bitumen is obtained as a by-product, it yields a valuable C.sub.5.sup.+ atmospheric distillate as a by-product. In view of the fact that when the former method is applied to asphaltic bitumen, yields are low, only the latter method is eligible for the preparation of heavy product with a low RCT from asphaltic bitumen or from mixtures of asphaltic bitumen and distillation residue. A drawback to the latter method, however, is that it gives rise to the formation of an undesirable C.sub.4.sup.- fraction which, moreover, contributes considerably to the hydrogen consumption of the process.
Applicants have carried out an investigation into the reduction of the RCT through catalytic hydrotreatment of mixtures of an asphaltic bitumen separated in the solvent deasphalting of a residue obtained in the distillation of a crude mineral oil (for the sake of brevity hereinafter referred to as "asphaltic bitumen I") and an asphaltic bitumen separted in the solvent deasphalting of a residue obtained in the distillation of a hydrotreated residual fraction of a crude mineral oil (for the sake of brevity hereinafter referred to as "asphaltic bitumen II"), which mixtures comprise less than 50 pbw of asphaltic bitumen II per 100 pbw of asphaltic bitumen I. This investigation has shown that, according as the catalytic hydrotreatment is carried out under more severe conditions in order to attain a greater RCT reduction, the parameter "C.sub.4.sup.- production per % RCT reduction" (for the sake of brevity hereinafter referred to as "G") at first remains virtually constant (G.sub.c) and subsequently shows a fairly sharp increase. In view of the hydrogen consumption of the process it is important to take care that the RCT reduction is not carried beyond the value corresponding to G=2.times.G.sub.c. This means that in practice there will be a number of cases in which it is undesirable, starting from a mixture of an asphaltic bitumen I and an asphaltic bitumen II, which mixture comprises less than 50 pbw of asphaltic bitumen II per 100 pbw of asphaltic bitumen I, to employ nothing but a catalytic hydrotreatment for preparing a product from which, after separation of an atmospheric distillate, an oil can be obtained which has an initial boiling point of T.sub.1 .degree.C. and an RCT of (a) %w. In those cases there is nevertheless an attractive manner of preparing an oil having the afore-mentioned initial boiling point and RCT from a mixture of an asphaltic bitumen I and an asphaltic bitumen II which mixture comprises less than 50 pbw of asphaltic bitumen II per 100 pbw of asphaltic bitumen I (for the sake of brevity hereinafter referred to as "residual feed mixture"). To this end the product obtained in the catalytic hydrotreatment is separated by distillation into an atmospheric distillate and an atmospheric residue having an initial boiling point of T.sub.1 .degree.C. The process may be continued in two ways. First, from the atmospheric residue so much asphaltic bitumen may be separated by solvent deasphalting that a deasphalted atmospheric residue obtained which has the desired RCT of (a) %w. Secondly, the atmospheric residue may be separated by distillation into a vacuum distillate and a vacuum residue, and from the vacuum residue so much asphaltic bitumen may be separated by solvent deasphalting that a deasphalted vacuum residue is obtained having an RCT which is such that when this deasphalted vacuum residue is mixed with the previously separated vacuum distillate, an oil is obtained which has the desired RCT of (a) %w. The most attractive balance between yields of: C.sub.4.sup.- fraction, C.sub.5.sup.+ atmospheric distillate, asphaltic bitumen and oil having an initial boiling point of T.sub.1 .degree.C. and an RCT of (a) %w is obtained when the catalytic hydrotreatment is carried out under such conditions that G lies between 1.5.times.G.sub.c and 2.0.times.G.sub.c. When the catalytic hydrotreatment is carried out under such conditions that G&lt;1.5.times.G.sub.c, a low C.sub.4.sup.- production is still obtained, but the yield of oil having an initial boiling point of T.sub.1 .degree.C. and an RCT of (a) %w in the combination process is unsatisfactory. When the catalytic hydrotreatment is carried out under such conditions that G&gt;2.0.times.G.sub.c, a high yield of oil having an initial boiling point of T.sub.1 .degree.C. and an RCT of (a) %w is still obtained in the combination process, but it is attended with an unacceptably high C.sub.4.sup.- production.
The investigation carried out by the applicants has shown that the RCT reductions in the catalytic hydrotreatment of a residual feed mixture, in which for G values are reached which correspond to 1.5.times.G.sub.c and 2.0.times.G.sub.c, are dependent on
(1) the desired initial boiling point of the oil having an RCT of (a) %w to be prepared (T.sub.1 .degree.C.), PA0 (2) the RCT of asphaltic bitumen I (b %w), PA0 (3) the average molecular weight of asphaltic bitumen I (M), PA0 (4) the RCT of asphaltic bitumen II (c %w), and PA0 (5) the asphaltic bitumen II/asphaltic bitumen I mixing ratio in the residual feed mixture, expressed in pbw of asphaltic bitumen II per 100 pbw of asphaltic bitumen I (r pbw), PA0 (a) The viscosity of the hydrocarbon mixture to be investigated is so high that it is impossible to determine the RCT by ASTM method D 524. In this case, the CCT (Conradson Carbon Test value) of the mixture is determined by ASTM method D 189, and the RCT is computed from the CCT according to the formula: EQU RCT=0.649.times.(CCT).sup.1.144 PA0 (b) The viscosity of the hydrocarbon mixture to be investigated is such that the RCT can still be determined according to the ASTM D 524 method, but this method gives an RCT value which lies above 20.0 %w. In this case, as in the case mentioned under (a), the CCT of the mixture is determined by ASTM method D 189 and the RCT is computed from the CCT according to the formula mentioned under (a). PA0 (c) The viscosity of the hydrocarbon mixture to be investigated is such that the RCT can be determined by ASTM method D 524 and this method gives an RCT value not higher than 20.0 %w. In this case the value thus found is taken to be the RCT of the mixture concerned.
and are given by a numerical relation.